Divinyl sulfone, diisocyanate, dicarboxylic acid or dihydroxysulfide reaction products with polyethylene ethers in high temperature pad dyeing and printing



nited States DIVINYL SULFONE, DIISOCYANATE, DICARBOX- YLIC ACID R DIHYDROXYSULFIDE REAC- TION PRODUCTS WITH POLYETHYLENE ETHERS IN HIGH TEMPERATURE PAD DYEING AND PRHJTING y s Robert Kuth and Hunswilli von Brachel, Cologne-Sulz, Germany, assignors to Farbenfabriken Bayer Aktie'ngesellschaft, Leverkusen, Germany, a German corporation s r No Drawing Filed Mar. 12, 19 62, Ser. No, 179,245

Claims priority, application Germany, Mar. 14, 1961,

9 Claims. (Cl. 8-55) five carbon atoms directly linked with one another.

As suitable polyethers there may be mentioned, for example, the condensation products obtainable, on the one hand, from polyethylene glycols, ethoxylated diand polyalcohols, ethoxylated diand polyphenols, ethoxylated monoand polyamines or ethoxylated diand polycarboxylic acids, and, on theother hand, from aliphatic, cycloaliphatic or aromatic dicarboxylic acids, thiodiglycol or other fl,fi'-dihydroxy-alkyl sulfides described, for example, in French patent specification No. 1,201,171. Furthermore, there may be mentioned the poly-addition products of polyethylene glycols or of ethoxylation products of the aforesaid kind and diand polyisocyanates, for example hexamethylene-diisocyanate, toluylene-diisocyanate, 4,4'-diisocyanate-diphenyl-methane, 4,4 diisocyanato-dicyclohexylmethane or w,w'-diisocyanatoxylene, or divinyl sulfones. Moreover, the mixed polymerisates may be taken into consideration which are obtainable from ethylene-oxide and cyclohexene-oxide or styrene oxide, optionally with the addition of propylene oxide, as well as the mixed polymerisates which are obtain-able from ethylene oxide and phenyl-glycide ether, ,cresyl-glycide ether, methoxy-phenyl-glycide ether or por mphenylene diglycide ether. Especially suitable are the polyethers obtained from the ethoxylation products of diphenols, in the first instance from the ethoxylation products from resorcinol, hydroquinone, 4,4'-dihydroxy-diphenyl-methane, 4,4 dihydroxy-diphenyl-propane and 4,4'-dihydroxy-diphenyl-sulfone.

In general, it is advantageous to use those polyethers which yield at least 1% solutions in water at room temperature. The water-solubility of polyethers increases with the increasing content of ether oxygen atoms and/ or hydrophilic groups such as hydroxyl groups, amino groups, ammonium groups, sulfoxide groups, sulfone groups, sulfonic acid groups or carboxylic groups.

The textile materials to be dyed with the aid of the process according to the invention may be based on a great variety of synthetic products such as, for example, polyacrylonitrile, the mixed polymerisates of acrylonitrile with other vinyl compounds as, e.g., acrylic esters, acryl amides, vinyl-pyridine, vinyl chloride or vinylidene chloride, polyamides as, e.g., polycaprolactam, polyadipic acid hexamethylene amide, poly-w-amino-undecanic acid, or polyurethanes or polyesters as, e.g., those from terephthalic acid and ethylene glycol or 1,4-dimethylol-cyclohexane.

I Par-sates Aug. 10, 1965 Furthermore, the process according to the present invention also comprises the dyeing of textile materials which are produced from cellulose esters, for example, from cellulose triacetate or butyrate. The process according to the invention may also be applied to mixed fabrics of synthetic fibres, or mixed fabrics of synthetic fibres and fibres of natu'ralorigin such aswool o'r cotton.

As with the known dyeing process mentioned above, dyestulis of a most varied type may also be used in the present a es); example, disperse dyestuffs, vat dyestulfs, acid wool "dyestuffs, metal complex dyestuffs or basic dyestufls. Mixed fabrics can be dyed by appropriate choice of the dy'es't'ulf from one or more baths, possibly by inserting an exhaust process, and also selectively, if desired. v

The polyethers to be used according to the invention are generally employed in quantities of 0.210%, preferably O.54%, referred to the padding solution or printing paste used. In general, they are added to the final pad ding solution or printing paste, but they may also be admixed to the dyestuifs The process according to the invention ensures a completely homogeneous dispersion of the dyestuffs before or after fixing. The absorptioriof the padding liquor, which is very difiicult when hydrophobic fibres are concerned, is improved; thus the otherwise required use of thickening agents which frequently retain the dyestutf, often entail the formation of dyestufi? conglomerates and give rise to a blocking of the dyeing apparatus becomes unnecessary. The polyethers appreciably improve the dyestutf yield, but above all they bring about unobjectionable dyeings even when several dyestuffs are used. Two-sidedness and runnings of the dyestuff at the selvedges of the dye ing are prevented. Moreover, the polyethers canbe washed out, and resist natural fibres where present.

In the process according to the invention other auxiliaries may also be used, for example softening agents in order to improve the handle of the textile materials, bydrotropic substances to increase the solubility of the dyestuffs in an aqueous bath,.or carrier to increase the penetration of the dyestuffs into the fibres.

A special method of carrying out the present invention consists in adding to the dyeing liquor in addition to polyethers containing groups condensable with formaldehyde such. as, for example resorcinol, hydroquinone, phenol or aniline groups, foifmaldehydeor compounds splitting off formaldehydeor methylol groups or methylol ether group-containing compounds. In this way the textile materials can be dyed in one bath and obtain an antistatic finish fast to washing.

The aforesaid satisfactory results cannot be attained to the same extent with the auxiliaries which have previously been proposed for the dyeing process concerned.

The following examples serve to illustrate the invention without, however, limiting tli'escope thereof. The dyestuffs designated in the examples by (a) to (e) are'explained in the list at the end of the description.

EXAMPLE 1 A fabric of polyethylene ter ephthalate fibers is impregnated on a foulard with a liquor containing per litre 20 g. of the dyestuli (a) and 20 g. of the polyether described below. The fabric is then squeezed to a weight increase of about 70% and dried at-10D? C.'in a suspension nozzle drier. For fixing the dyeing, the fabric is subsequently treated for 60 seconds at 190', C. withhot air in the same apparatus or in a tentering frame, then rinsed and washedwith hot water. g I 1 The fabric shows an entirely uniform and unobjectionable fixed yellow dyeing. The shade is fuller than that of a dyeing which can be attained with the use of the same dyestufi amount (referred to the fabric) according to the polyether described in Example 1.

the known therrriosol process or to the exhaust process while using commercial carriers.

The polyether used is obtained as follows: Ethoxylated resorcinol of molecular weight 1100 is condensed with thiodiglycol in a molecular ratio of 111.8 in the presence of 1 percent by weight of phosphoric acid at a temperature of 180-185" C., first under normal pressure, then in a vacuum at to mm. Hg, until a hydroxyl number of to 22 is obtained.

EXAMPLE 2 As described in Example 1 a fabric of polyethylene terephthalate fibres is treated with a liquor containing per litre g. of the dyestuif (a), 5 g. of the dyestutf (b), and 3 g. of the dyestutf (c) as well as 20 g. of

After the customary finish the so-treated fabric shows an entirely even brown shade. Without using the polyether an uneven dyeing is obtained on which the individual dyestuff components are distinctly to be seen.

EXAMPLE 3 A fabric of polyacrylonitrile filaments is treated, as described in Example 1, with a liquor containing per litre 3 g. of the dyestutf (a), 20 g. of the polyether described in Example 1, 8 g. of the condensation product from octaethylene glycol and dimethylol urea as well as 2 g. of butyl-naphthalene sulfonic acid.

After the customary finish, the fabric shows an even blue shade, and it possesses morover an antistatic finish which is fast to washing. Even after 10 washings with conventional mild detergents the surface resistance is 10 times lower than that of untreated fabric.

EXAMPLE 4 A fabric of polyacrylonitrile filaments is treated with a liquor containing per-litre 2.5 g. of the dyestutf (d), 20 g. of the polyether described below and 2.7 g. of ethoxylated oleyl alcohol. The fabric is subsequently heated to 180 C. for 1 minute in order to fix the dyeing. The red pastel shade obtained is entirely even, and the fabric possesses a full soft handle. The polyether used is prepared by addition of ethoxylated resorcinol of molecular weight 1250 to divinyl sulphone in a molecular ratio of 7:6 in the presence of sodium methylate as catalyst.

EXAMPLE 5 A fabric of polycaprolactam is treated with a solution containing per litre g. of the chromium complex of the dyestuff (e) and 25 g. of the polyether described below. For fixing of the dyeing, the fabric is heated to 192 C. for 70 seconds. Colorimetric analysis shows that the dyestuff yield is higher by 40% than that obtained with the use of a solution containing no polyether.

The polyether used is produced by addition of ethoxylated resorcinol of molecular weight 1300 to hexamethylene diisocyanate in a molecular ratio of 7: 6.

EXAMPLE 6 A mixed fabric of polyethylene tercphthalate fibres and 45% wool is dyed as described in Example 1,

with a liquor containing per litre 25 g. of the dyestuff (c), 4 g. of the dyestufii (d), 3 g. of the dyestuff (e), 20 g. of the sulfoxide group-containing polyether described below, 4 g. of butyl-naphthalene-sulfonic acid sodium salt and 4 g. of butyl-naphthalene-sulfonic acid. The navy blue dyeing obtained on the polyester portion of the fabric shows no runnings at the selvedges or ends, the wool portion which is not stained is subsequently dyed on the winch in known manner with usual wool dyestuffs also yielding a navy blue dyeing so that an evenly dyed navy blue cloth is obtained. After working up 400 metres of the fabric there are not to be found any sublimed or mechanically rubbed off dyestutf particles neither on the suspension nozzle drier nor in the pin beds of the tendering frame.

The polyether used is produced by oxidation'of the polyether described in Example 1 with 1 mol of the hydrogen peroxide per mol of the thiodiglycol contained in the polyether.

EXAMPLE 7 A polyethylene terephthalate band such as is used for safety belts, is dyed with a liquor. containing per litre 30 g. of the dyestutf (c), 3.5 g. of the dyestuif (d), 13 g. of the dyestuff (e), 20 g. of the polyether described below, and 2 g. of butyl-naphthalene-sulfonic acid. The dyeing method corresponds to the mode of operation indicated in Example 1, with the exception that the band is squeezed to a weight increase of 30%. A grey dyeing is obtained which, after a reductive after-treatment, is distinguished by good fastuess properties and an especially good penetration.

The polyether used is produced by condensing ethoxylated resorcinol of molecular weight 1700 with di-(B- hydroxypropyl)-sulfide in a molecular ratio of 1:3 until a molecular weight of 6400 is attained.

Example 8 -A fabric of polyethyleneterephthalate fibres is impregnated on the foulard with a liquor containing per litre g. of the dyestutf (c), 30 g. of the polyether described below, and 3 g. of methylene-bis-naphthalene sulfonic acid sodium salt.

After squeezing the material to a weight increase of about 70%, the fabric is dried as described in Example 1, and the dyeing subsequently fixed. An unobjectionably fixed, brilliantblue dyeing is obtained which, after a reductive after-treatment with a liquor containing per litre 3 g. of a sodium hydroxide solution and 2 g. of hydrosulfite, has an outstanding fastness to rubbing. The dyestutf yield is higher by about 50% than that obtained by a control experiment carried out in the absence of the polyether according to the invention;

The polyether used is obtained by heating to C. for four hours ethoxylated N-methyl-ethanol-amine of molecular weight 1000, with hexamethylene-di-isocyanate in a molecular ratio of 100:92.

Instead of the polyether described above, there can be used with the same good result a polyether obtained by heating ethoxylated N-butyl-diethanol-amine of molecular weight 1200 with sebacic acid until thernolecular weight of the product formed amounts to 5000.

List of the dyestufls We claim: I

1. In a process for dyeing and printing synthetic textile materials and blends thereof with natural fibers by coloring the textile materials with a dyeing member selected from the group consisting of a padding dyebath preparation and dye printing paste, applying the dyeing member to the textile materials and fixing by heating to a temperature of at least C., the improvement consisting in applying to said textile materials and blends thereof, said dyeing member and an active amount of apolyether selected from the group consisting of (I) the reaction product of a first member consisting of a polyethylene oxide ether of dihydroxy benzene with a second member selected from the group consisting of (a) a p,B'-dihydroxy-alkyl-sulfide 6. The process of claim 1 wherein the polyether con- (b) adiisocyanate and sists of the reaction product of ethoxylated resorcinol (c) a divinyl sulfone, and with hexamethylene diisocyanate.

(II) the reaction product of a first member consisting 7. The process of claim 1 wherein the polyether conof polyoxyethylene ethers of polyalkanol amines 5 sists of the oxidation product obtained by means of hywith a second member selected from the group condrogen peroxide from the reaction product of ethoxylated sisting of resorcinol with thiodiglycol.

(a) adiisocyanate, and 8. The process of claim 1 wherein the polyether con- (b) a dicarboxylic acid, said product having at sists of the reaction product of ethoxylated N-inethylleast two hydroxyl groups; said first members 1 ethanolamine with hexamethylene diisocyanate.

repeatedly alternating with the second members 9. The process of claim 1 wherein the polyether conin the condensation product, one of said memsists of the reaction pr d of h ylated N-butylbers containing not less than 5 carbon atoms diethanolam-ine with sebacic acid.

directly linked with one another.-

2. The process of claim 1 wherein the polyether is 15 References Cited by the Examiner employed in a concentration of .2%10% referred to the UNITED STATES PATENTS dyeing component.

3. The process of claim 1 wherein the polyether con- 325823;? a1 X sists of the reaction product of ethoxylated resorcinol 2963513 12/60 Albrecht X with thiodiglycol. 2

4. The process of claim 1 wherein the polyether con- OTHER REFERENCES sists of the ereaction product of ethoxylated resorcinol A i Dyestufi Reporter, 1949, p. 593.

with di-(;8-hydroxypropyl)-sulfide.

5. The process of claim 1 wherein the polyether con- NORMAN TORCHIN Pr'mm Exammer' sists of the reaction product of ethoxylated resorcinol 25 MORRIS O. WOLK, A LOUIS MONACELL, with divinyl sulphone. Examiners. 

1. IN A PROCESS FOR DYEING AND PRINTING SYNTHETIC TEXTILE MATERIALS AND BLENDS THEREOF WITH NATURAL FIBERS BY COLORING THE TEXTILE MATERIALS WITH A DYEING MEMBER SELECTED FROM THE GROUP CONSISTING OF A PADDING DYEBATH PREPARATION AND DYE PRINTING PASTE, APPLYING THE DYEING MEMBER TO THE TEXTILE MATERIALS AND FIXING BY HEATING TO A TEMPERATURE OF AT LEAST 180*C., THE IMPROVEMENT CONSISTING IN APPLYING TO SAID TEXTILE MATERIALS AND BLENDS THEREOF, SAID DYEING MEMBER AND AN ACTIVE AMOUNT OF A POLYETHER SELECTED FROM THE GROUP CONSISTING OF (I) THE REACTION PRODUCT OF A FIRST MEMBER CONSISTING OF A POLYETHYLENE OXIDE ETHER OF DIHYDROXY BENZENE WITH A SECOND MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) A B,B''-DIHYDROXY-ALKYL-SULFIDE (B) A DIISOCYANATE AND (C) A DIVINYL SULFONE, AND (II) THE REACTION PRODUCT OF A FIRST MEMBER CONSISTING OF POLYOXYETHYLENE ETHERS OF POLYALKANOL AMINES WITH A SECOND MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) A DIISOCYANATE, AND (B) A DICARBOXYLIC ACID, SAID PRODUCT HAVING AT LEAST TWO HYDROXYL GROUPS; SAID FIRST MEMBERS REPEATEDLY ALTERNATING WITH THE SECOND MEMBERS IN THE CONDENSATION PRODUCT, ONE OF SAID MEMBERS CONTAINING NOT LESS THAN 5 CARBON ATOMS DIRECTLY LINKED WITH ONE ANOTHER. 